Advances in Inorganic Chemistry (eBook)

Cover 1
Contents 6
Preface 10
Chapter 1. Dioxygen Activation by Transition Metal Complexes. Atom Transfer and Free Radical Chemistry in Aqueous Media 12
I. Introduction 12
II. Preparation and Characterization 14
III. Reactivity 23
IV. Conclusions and Future Directions 61
V. Abbreviations 63
References 63
Chapter 2. Redox Reactivity of Coordinated Ligands in Pentacyano(L)Ferrate Complexes 72
I. Introduction 72
II. General Properties of the Nitroprusside ion, [Fe(CN)5NO]2– (NP), and Related Nitrosyl Complexes 75
III. The Coordination Chemistry of NO. Formation and Dissociation Reactions 77
IV. The Redox Reactivity of Bound NO 86
V. The Electrophilic Reactions of Bound NO 90
VI. The Autooxidation of Hydrazine 115
VII. The Oxidation of Amines and Alcohols 117
VIII. The Disproportionation of Hydroxylamine 119
IX. Miscellaneous Reactions 121
X. Conclusions 131
References 133
Chapter 3. Carbonato Complexes: Models for Carbonic Anhydrase 138
I. Introduction 139
II. Carbonic Acid, Bicarbonate, and Carbonate 140
III. The Chemistry of Metal Carbonates 144
IV. Kinetics and Mechanism of Formation and Aquation/Decarboxylation Reactions 156
V. Discovery and Classification of Carbonic Anhydrases 170
VI. Structure of a-Class Carbonic Anhydrase from Human Erythrocytes (the High Activity form HCA II) 172
VII. Structure of ß-Carbonic Anhydrase from the Red Alga, Porphyridium purpureum 191
VIII. Structure of .-Class Carbonic Anhydrase of Methanosarcina thermophila (Cam) 194
IX. A d-Class of Carbonic Anhydrase? 196
X. Model Chemistry 197
XI. Concluding Remarks 199
XII. Abbreviations 200
References 201
Chapter 4. Transition Metal Chemistry of Glucose Oxidase, Horseradish Peroxidase, and Related Enzymes 212
I. Introduction 212
II. Enzymes 214
III. Properties of Mediators 219
IV. Ferrocenes 221
V. Osmium and Ruthenium Compounds 250
VI. Chiral Complexes 264
VII. Cyclometalated Ruthenium(II) and Osmium(II)Mediators 268
VIII. Concluding Remarks 273
References 273
Chapter 5. Properties of Transition Metal Complexes with Metal–Carbon Bonds in Aqueous Solutions as Studied by Pulse Radiolysis 282
I. Introduction 283
II. Radiolysis of Aqueous Solutions 283
III. Reaction of Aliphatic Carbon-Centered Radicals with TransitionMetal Complexes in Aqueous Solutions 285
IV. Formation of Transition Metal Complexes with Metal–Carbon s-Bonds 286
V. Properties of Complexes with Metal–Carbon s-Bonds 289
VI. Mechanisms of Decomposition of the Transient Complexes LmMn+1–R 291
VII. Alkene Complexes 309
VIII. Complexes with Metal–Carbon s-Bonds Formed in Redox Processes Between Transition Metal Complexes and Organic Substrates 310
IX. Elucidation of the Mechanisms of Catalytic Processes 315
References 319
Chapter 6. Transition Metal Complexes with Bis(Hydrazone) Ligands of 2,6-Diacetylpyridine. Hepta-Coordination of 3d Metals 326
I. Introduction 326
II. Aspects Studied 327
III. Concluding Discussion 361
References 367
Chapter 7. Potential Applications for the Use of Lanthanide Complexes as Luminescent Biolabels 372
I. Scope 372
II. Introduction 373
III. Properties of Lanthanide(III) Ions 374
IV. Ligand Systems Explored 380
V. Biochemical Applications 401
VI. Concluding Remarks 428
VII. Glossary 428
References 430
Index 444
Contents of Previous Volumes 454